Production of ornamental multitone effect on polyamide textile materials

ABSTRACT

A METHOD FOR PRODUCING AN ORNAMETAL MULITONE EFFECT ON A POLYAMIDE TEXTILE MATERIAL WHICH COMPRISES PADDING THE SURFACE OF SAID POLYAMIDE TEXTILE MATEIALLY LOCALLY WITH A DYE RATE CONTROLLING AGENT, FIXING SAID DYE RATE CONTROLLING AGENT ON SAID POLYAMIDE FIBER, WASHING THE SO-TREATED POLYAMIDE FIBER SO AS TO FORM AREAS HAVING DIFFERING RATES OF DYEING AND THEREAFTER DIP DYEING SAID MATERIAL WITH ANIONIC DYESTUFF.

United States Patent US. Cl. 8-14 8 Claims ABSTRACT OF THE DISCLOSURE 'A method for producing an ornamental multitone effect on a polyamide textile material which comprises padding the surface of said polyamide textile materially locally with a dye rate controlling agent, fixing said dye rate controlling agent on said polyamide fiber, washing the so-treated polyamide fiber so as to form areas having differing rates of' dyeing and thereafter dip dyeing said material with anionic dyestuff.

This invention relates to the production of ornamental multitone effect on polyamide textile materials. More particularly, this invention relates to accomplishing in a single stroke the dyeing of polyamide materials with a multitone effect of at least two stages, i.e., dyed partly to a deep shade and partly to a light shade of the same color, or left white (hereinafter the light shade inclusive of white to be referred to as light shade).

Heretofore as a method of accomplishing the multitone dyeing with the textile material, said material (either yarn or fabric) was wrapped or adhered together with aluminum foil followed by steaming, thereby creating a difference in the dye absorbability between the portions which were either wrapped or not wrapped with the aluminum foil, after which the aluminum foil was removed and the textile material was dyed. In another method mottled yarns were made by tying the yarn to be dyed locally with another yarn thereby impeding the penetration of the dye to those parts which were tied and then dyeing the tied yarn. These methods however had the drawback that there was a need of such troublesome steps as wrapping with aluminum foils or tying with a yarn.

Again, there is a method in which the dyeing is carried out after first printing the textile material with a printing paste containing a thickening agent in which has been incorporated either an adsorbent, such as kaolin and active carbon, or a reducing agent, such as zinc powder. In this method it is however diflicult to obtain level dyeing results owing to either cracking or falling off of the paste, since in this method the dyeing must be performed in the pasteadhered state. In addition, if the material is to be dyed after knitting or weaving, the knitting or weaving is diflicult to perform because of the presence of the paste. On the other hand, if the knitting or weaving is to be carried out after dyeing, this is also diflicult, since fiulfs and naps develop during the dyeing operation. As a matter of fact, multitone knitted or woven fabrics cannot be obtained by this method.

This invention provides a method whereby the foregoing drawbacks of the prior art methods are eliminated and an ornamental multitone effect on polyamide textile materials is readily produced with the respective deep and light areas being dyed levelly.

This invention is based on a principle which consists 3,669,611 Patented June 13, 1972 of forming on a polyamide textile material with the aid of dyeing rate controlling agents areas having different dyeing rates, and thereafter dyeing the material. Namely, this invention comprises either padding the surface of a polyamide textile material locally with one class of dyeing rate controlling agent having aifinity for polyamide fibers or padding differing surface areas of a polyamide textile material with at least one of aforesaid dye rate controlling agents in a controlled manner so that the dyeing rates will vary respectively, with a result that at least two different dyeing rates result with respect to the treated areas and a third rate is effected with respect to the untreated areas fixing said dye rate controlling agent on the polyamide fibers, followed by Washing the material thereby forming on said polyamide textile material areas having differing dyeing rates, and thereafter dyeing the material in customary manner using an anion dyestuff.

The term dye rate controlling agent, as used herein, refers to an assistant which has either an action of increasing or decreasing the rate of dyeing to a marked degree and/or an action of increasing or decreasing markedly the amount of dye adsorption. Those having an increasing action are referred to as accelerating agents, while those having a decreasing action are referred to as retarding agents. The compounds used as accelerating agents are generally referred to also as swelling agents of polyamide fibers, and included are the various compounds which are known to have the action of accelerating the diffusion of dyestuffs into these fibers. Specific examples included phenol, methylnaphthalene, cresol, phenylphenol chlorophenol and benzylalcohol. On the other hand, as the aforesaid retarding agents, all of the various chemicals which are known generally as fixing agents for enhancing the wet color fastness of dyed polyamide textile materials can be used in this invention. Namely, when polyamide textile materials were padded with these fixing agents prior to their dyeing, we found that they had the effect of decreasing greatly the amount of dye adsorption. This finding constitutes a part of the basis of this invention. Specific examples of the retarding agents include tannin and the so-called synthetic tannins. Synthetic tannins are exemplified by the following:

Compounds consisting of sulfurized phenols (the term phenols, as here used, refers to the compounds having benzene nucleus with a hydroxy group, such as phenol, cresol, resorcinol, chlorophenol, phenylphenol and salicyclic acid; This to apply likewise hereinafter.); sulfonic acids of sulfurized phenols; condensation products of sulfonated phenols and formaldehyde; condensation products of benzylchloride and sulfonated naphthalene; products obtained by reacting phenols with sulfur and alkaline salts (the alkaline metal salts whose aqueous soutions exhibit alkalinity, e.g., caustic potash, sodium carbonate and sodium sulfide) and thereafter reacting therewith acid sodium sulfite and formaldehyde; anionic aqueous polycondensates obtained by heating either bisphenol sulfone or the derivatives thereof with either aromatic sulfonic acids or aromatic carboxylic acids in the copresence of formalin; the alkali or ammonium salts of the condensation products of lower aldehydes and sulfonated dihydroxydiphenyl sulfone; and condensation products of either bisphenol sulfone or derivatives thereof or bisphenol A or derivatives thereof with acid sodium sulfite and formalin.

In padding the polyamide textile material with the aforesaid dyeing rate controlling agents, a convenient procedure is to use them. either in the form of a printing paste consisting of a mixture of said controlling agents with thickening agents or in the form of a solution of the controlling agents in a solvent, i.e., water or organic solvents. The printing paste form is convenient for padding in the case of either a tow, yarn, or fabric, whereas the solution form is suitable for padding a tow or yarn. The thickening agent to be used are the watersoluble thickening agents usually used in the art and include the modified natural gums such, for example as crystal gum and etherified locust bean gum, and the emulsion pastes such, for example, as oil-in-water emulsions and water-in-oil emulsions. A viscosity of the printing paste ranging betwen 500 and 20,000 centipoises is preferred. The organic solvents to be used for dissolving the dyeing rate controlling agent are preferably those which are miscible with the controlling agent and in addition possess per se a property of drying rapidly. As specific examples of these organic solvents, there can be mentioned the ketone type solvents such as acetone, aliphatic alcohols of 1-3 carbon atoms, the alkyl esters of lower fatty acids, such as ethyl acetate, and the like. Water and these organic solvents can be used either singly or as mixtures thereof. Again, it is also possible to use conjointly a small amount of those solvents which have relatively high boiling points and are good solvents of said controlling agents, such, for example, as ethylene glycol, thio'diethylene glycol and glacial acetic acid. In using these solvents, a small amount of a thickening agent may also be incorporated. Thus, the cohesiveness of the yarn being treated can be enhanced and the operations facilitated.

The concentration in which the dye swelling agent is to be mixed with the hereinabove-described thickening agent is preferably a range 1-50% by weight.

In padding the polyamide textile material \m'th the paste or solution containing the aforesaid thickening agent, the variouscustomary procedure can be employed. Namely, in the case of a printing paste, the padding can be by either the screen printing system, roller printing system or the melang printing system. On the other hand, in the case of a solution, the padding can be by either the melang printing system or the spraying system.

As hereinabove described, the dyeing rate controlling agent is applied locally to different surface areas of the polyamide textile material. When the surface of the polyamide textile material is padded locally with only one class of the dyeing rate controlling agent, a difference in the rate of dyeing takes pace between the areas which have or have not been padded with the controlling agent, and hence when this material is subsequently dyed, a two-tone shade is correspondingly produced in the two areas. On the other hand, for forming areas which can be dyed, as desired, with a pattern of a multitone of three or more tones, at least one dyeing rate controling agent is used, which is applied correspondingly to said areas in modes such that two or more different dyeing rates are obtained. The modes of operation are as follows: In one of the modes both an accelerating agent and a retarding agent are used, which are applied respectively to the different areas. In another mode the padding is carried out while varying the concentration of the accelerating or retarding agent in the paste or solution. When the concentration of the retarding agent is varied, a great difference in the dyeing rates in demonstrated, but in the case of the acceleratnig agent, this difference is not pronounced. Thus, as a practical matter, the procedure of using the retarding agent with changes in its concentration is the more effective method. In a still another mode it is possible to utilize the differences in dyeing rate that are demonstrated by the different classes of compounds of the accelerating or retarding agent.

For fixing the padded dyeing rate controlling agent on the fibers of the polyamide textile material, the material is heat terated. The heat treatment can be carried out by means of dry heating or steaming, and the fixing is achieved effectively in 20 seconds to 30 minutes at a temperature -200" C. Especially desirable conditions in the case of dry heating is a temperature of -190" C. for 20 seconds to 10 minutes, and in the case of steaming, a temperature of 100-120" C. for 5-30 minutes. When tannin has been used as the retarding agent, the fixing can be achieved still more completely, if the material, after heat treatment, is further treated for 5-20 minutes at 60-80 C. in a bath containing 0.1-0.4 gram per liter of tartar emetic.

After the foregoing fixing step, the material is washed. The washing can be carried out by the usual washing with Water or by soaping. The washing serves to remove the dyeing rate controlling agent, if any, which has not been completely fixed, as well as the thickening agent used. If the dyeing rate controlling agent remains, it falls off during the subsequent dyeing step either to impede the adsorption of the dye or become the cause of spotty dyeing. On the other hand, if the thickening agent remains, this likewise falls off during the dyeing step and become the cause of spotty dyeing. Further, for instance, if it is intended to weave or knit the so-fixed tow or yarn and then dye it, adverse effects are bad in accomplishing the smooth operation of weaving or knitting on account of the adhering thickening agent. When the dyeing rate controlling agent has been applied to the tow or yarn in solution form, the tow or yarn can either be woven or knitted first and then the fixing be performed or thefixing step can be carried out first and then the tow or yarn be woven or knitted followed by washing.

These fixing and washing steps are steps which were not, or could not, be carried out in the prior art methods of dyeing textile materials and is hence a feature of this invention.

The polyamide textile material which has been treated as hereinbefore described is then dyed by the customary dip dyeing procedure. The dyestuffs used include the anion dyes such as acid dyes, acid mordant dyes, direct dyes and reactive dyes. The disperse dyes do not give the desired results. Those which are suitable for the various dyestuffs are exemplified below:

Acid dyes:

C.I. Acid Yellow 99 (C.I. 13900), C.I. Acid Red 32 (C.I. 17065), C.I. Acid Violet 12 (C.I. 18075), C.I. Acid Blue 23 (C.I. 61125) and C. 1. Black 54 (C.I. 14885).

Acid mordant dyes:

C.I. Mordant Yellow 5 (C.I. 14130), ClI. Mordant Red 7 (C.I. 18760), C.I. Mordant Blue 47 (C.I. 43855), C.I. Mordant Brown 6 (C.I. 11875) and C.I. Mordant Black 15 (C.I. 15690).

Direct dyes:

C.I. Direct Yellow 1 (C.I. 22250), C.I. Direct Red (C.I. 22310), C.I. Direct Violet 1 (0.1L 22570), C.I. Direct Blue 1 (C.I. 2441 0) and C.I. Direct Black 4 (C.I. 30245).

Reactive dyes:

C.I. Reactive Yellow 1, C.I. Reactive Red 1, C.I. Reactive Violet 1, C.I. Reactive Blue 1 and C.I. Reactive Black 1.

Typical dyeing conditions are presented below: In the case of acid, direct and reactive dyestuffs: Concentration of the dye used in the case of light to medium shades, 3% (O.W.F.=on weight of fiber), in the case of deep shades, 3-6% (O.W.F.) and in the case of black, 6-8% (O.W.F.). The dye is dissolved in boiling water, to which are then added 2-5% (O.W.F.) of glacial acetic acid or formic acid and 10-20% (O.W.F.) of sodium sulfate. A bath ratio of 1:20-100 is employed. The polyamide textile material is introduced into the foregoing dye bath at about 40 C. and brought to the boil in 30' minutes, at which temperature it is dyed for 30-60 minutes.

In the case of acid mordant dyes: The material to be dyed is introduced into a dye bath whose bath ratio is 1:20-100 and containing, in accordance with the deepness or lightness of the color phase desired, 16% (O.W.F.) of the dye, 2-5% (O.W.F.) of glacial acetic acid and -20% (O.W.F.) of sodium sulfate, following which the temperature of the bath is gradually raised and brought to the boil in 45 minutes, at which temperature the dyeing is carried out for about 30 minutes until the dyestufi is exhausted. Following this, the temperature of the dye bath is lowered to about 70 C., and then after adding 0.23% of potassium or sodium bichromate, the material is boiled for 30-60 minutes to complete its dyeing.

Thus the polyamide textile material is dyed by the same dyestutf in deep and light shade corresponding to the areas to which the dyeing rate controlling agent has been fixed with varying dyeability rate. Hence, the product presents a pattern having ornamental multitone shades. By a suitable choice of the configurations of the aforesaid areas, patterns of any desired configuration can be obtained.

The invention method can be applied to fibers, tows, yarns, threads, woven fabric, knitted fabrics, nonwoven fabrics and other textile materials composed of polyamides. And it is especially an important feature and advantage of this invention that it can be applied very effectively also to the thick and pile fabrics such as carpeting.

This invention is illustrated more specifically by means of the following nonlimitative examples.

EXAMPLE 1 A 224 filament 4200 total denier textured 6 nylon yarn was locally screen printed in different areas thereof with respectively the following accelerating and retarding agent pastes. The length of the portions treated in this case with either the accelerating or retarding agent paste was about one centimeter, leaving nontreated portions at intervals of about 2 cm. The treatment with the accelerating and retarding agent pastes were carried out in turn. After drying, the varn was steamed for 20 minutes at 100 C.

1 See formula below The yarn was then washed with water and thereafter dyed for 30 minutes at 70 C. in a dye bath of a bath ratio 1:100 and consisting of 2% (O.W.F.) of C.I. Yellow 99 (C.I. 13900) and 2% (O.W.F.) of ammonium acetate. Thus was obtained a yarn having an ornamental threetone yellow shade.

EXAMPLE 2 A 112 filament 2100 total denier 66 nylon yarn was melang printed locally in different portions with the following accelerating and retarding agent solutions, after which it was knitted into tricot.

Percent Methylnaphthalene 5 Acetone Sulfurized phenol (presumed formula) 1 4 Ethyl alcohol 46 Water 50 1 See formula below:

Tricot knit structure:

Percent Condensation product of cresol sulfonic acid and formaldehyde (presumed formula) 1 4 Thiodiethylene glycol 4 Urea 10 Octyl alcohol 2 Water 30 Etherified locust bean gum (12%) 50 1 See formula below:

OH "I CH3 CH3 After drying, the yarn was steamed for 20 minutes at 100 C. followed by washing with water and thereafter dyeing for 30 minutes at 70 C. in a dye bath of bath ratio 1:100 and consisting of 2% (O.W.F.) of C.I. Violet 12 (C.I. 18075) and 2% (O.W.F.) of ammonium acetate. Thus a yarn having an ornamental two-tone violet shade was obtained.

EXAMPLE 4 A 24 filament 50 total denier 66 nylon yarn was roller printed locally with following two classes of printing pastes.

Paste 1 Percent Condensation product of resorcinol and formaldehyde (presumed formula) 1 4 Thiodiethylene glycol 4 Urea 10 Octyl alcohol 2 Water 30 Etherified locust bean gum (12%) 50 1 See formula below:

Paste 2 Percent Condensation product of resorcinol and formaldehyde (the same formula as above) 1 Thiodiethylene glycol 4 Urea 10 Octyl alcohol 2 Water 30 Etherified locust bean gum (12%) 50 After drying, the yarn was steamed for 20 minutes at 100 C. followed by washing with water and thereafter dyeing for 30 minutes at 70 C. in a dye bath of a bath ratio 1:100 and composed of 2% (O.W.F.) of Cl. Acid Blue 23 (Cl. 61125) and 2% (O.W.F.) of ammonium acetate. The so obtained yarn has an ornamental threetone blue shade.

EXAMPLE A 48 filament 100 total denier yarn of 6 nylon was melang printed locally with the retarding agent solution indicated below, following which it was steamed for 20 minutes at 100 C.

Percent Condensation product of benzyl chloride and naphthalene sulfonic acid (presumed formula) 1 4 Acetone 96 1 See formula below.

The Yarn is then knitted into tricot.

Back: Yarn of 6 nylon. Structure 2310 Front: Yarn of 6 nylon. Structure 1012 Pattern: Reverse half tricot stitch Following this, the yarn was dyed for 30 minutes at 80 C. in a dye bath of a bath ratio 1:100 and consisting of 1% (O.W.F.) of CI. Acid Black 54 (Cl. 14885). Thus a fabric having an ornamental two-tone black shade was obtained.

EXAMPLE 6 A 34 filament 200 total denier yarn of 6 nylon was sprayed locally with the following retarding agent solution, after which it was steamed for 20 minutes at 100 C. The so treated yarn was then knitted into tricot of the below-described structure.

Percent Tannin 4 Ethyl alcohol 96 Back: Yarn of acetate. Knit structure 1023 Front: Yarn of 6 nylon. Knit structure 0110 Pattern: Striped sharkskin EXAMPLE 7 A 34 filament 200 total denier 66 nylon yarn was melang printed locally with the retarding agent solution of a composition as indicated below.

Percent Synthetic tannin 1 10 Sodium salt of lauryl sulfuric acid ester (surfactant) 2 Water 1 Synthetic tannin: A compound obtained by reacting 4,4- dihydroxy-diphenyl-2,2-propane, sulfur, caustic potash, water, acid sodium sulfite and formaldehyde, and presumably having the formula (l)Na I dNa The yarn was then dry heated for 5 minutes at 100 C., after which it was woven into a plain fabric (warp 75 ends/inch, weft 50 ends/inch). The resulting fabric was then dyed for 60 minutes at C. in a dye bath of a bath ratio 1:100 and consisting of 3% (O.W.F.) of Cl. Acid Red 115 (CI. 27200). Thus a fabric having an ornamental two-tone red shade was obtained.

EXAMPLE 8 The plain fabric described in Example 7 was screen printed locally with the accelerating and retarding agent pastes indicated below. The pattern of the two screen stencils used in printing the accelerating and retarding agent pastes consisted of polka dots 1 cm. in diameter which were disposed latticelike with the dots at a given interval, the distance between the centers of the dots being 3 cm. The accelerating and retarding agent pastes were printed in alternation ensuring that they were not printed one on top of the other. After printing, the fabric was immediately treated with hot air for 2 minutes at C.

Percent Phenol 5 Water 45 Sodium alginate (6%) 50 Condensation product of bisphenol sulfone, naphthalene sulfonic acid and formaldehyde (presumed formula) 1 4 Glacial acetic acid 1 Thiodiethylene glycol 4 Octyl alcohol 1 Urea 10 Water 5 30 Crystal gum(33%) 50 1 See formula below:

soz I Q i. [p

The fabric was then Water-washed and thereafter dyed for 30 minutes at 80 C. in a dye bath of a bath ratio 1:100 and consisting of 1% (O.W.F.) of Cl. Direct Red 1 (CI. 22210) and 2% (O.W.F.) of ammonium acetate.

Thus a fabric having an ornamental three-tone red shade was obtained.

EXAMPLE 9 A plain fabric (warp 100 ends/inch, weft 75 ends/ inch) obtained using a 24 filament 100 total denier yarn of -6 nylon Was screen printed locally with the printing paste indicated below.

Percent 4,4 dihydroxy 3,3',S-trimethylol-5-sulfomethyl-diphenyl-2,2-propane (presumed formula) 1 4 Glacial acetic acid 1 Thiodiethylene glycol 4 Octyl alcohol 1 Urea 10 Water '30 Crystal gum (33%) 50 100 1 See formula below:

HOCHB 0111250311 H OH I (EH3 g HOCHz H2011 After printing, the fabric was dry heated for 2 minutes at 100 C., then Washed with water and thereafter dyed for 30 minutes at 80 C. in a dye bath at a bath ratio 1:100 and consisting of 1% (O.W.F.) of Cl. Reactive Red 1 and 2% (O.W.F.) of ammonium acetate to obtain a fabric having an ornamental two-tone red shade.

EXAMPLE 10 The plain fabric used in Example 9 was screen printed locally with the following printing pastes.

Percent Synthetic tannin 1 10 Glacial acetic acid 1 Thiodiethylene glycol 4 Octyl alcohol 1 Urea 10 Water 24 Crystal gum (33%) 50 Tannin 2 Glacial acetic acid 1 Thiodiethylene glycol 4 Octyl alcohol 1 Urea 10 Water 29 Crystal gum (33%) 50 1 Synthetic tannin: A condensation product obtained by reacting phenol, caustic soda, sulfur and acid sodium sulfite in the presence of formaldehyde, the formula of which is presumed to be as follows ONa ONa 1 I s C gSO Na C ZSOENa 3-10 10 EXAMPLE 11 A 24 filament 50 total denier yarn of 6 nylon was melang printed locally with the following accelerating agent solution.

Percent Phenol 5 Acetone The yarn was then knitted into tricot having the following structure.

Back: 24 filament (50 denier) yarn of polyester Structure Front: The aforesaid 6 nylon yarn. Structure 0110 Pattern: Striped sharkskin.

After knittingfthe fabric was treated with dry heat for 5 minutes at 100 C. Thereafter it was dyed for 30 minutes at 80 C. in a dye bath of a bath ratio 1:100 and consisting of 1% (O.W.F.) of CI. Acid Blue 23 (CI. 61125) and 2% (O.W.F.) of ammonium acetate. Thus, a fabric having an ornamental two-tone blue shade was obtained.

EXAMPLE 12 Example 1 was repeated except that there was used instead of 4% of sulfonated vulcanized phenol, 10% of a condensation product of formaldehyde and a sulfonated product of 4,4-dihydroxy diphenyl sulfone, whose formula is presumed to be as follows:

As a result, an ornamental three-tone yellow shade was obtained.

EXAMPLE 13 Instead of 4% of sulfonic acid of sulfurized phenol of Example 1, there was used 10% of a sulfomethylated product of 4,4'-dihydroxy diphenyl sulfone, whose formula is presumed to be as follows:

Hosoi OH CHzSOgNa CHzSO Na The experiment was otherwise carried out as in Example 1, with the consequence that an ornamental three-tone yellow shade was obtained.

We claim:

1. A method of producing an ornamental multitone effect on polyamide textile materials, which includes the sequence of steps:

(a) padding the surface of said polyamide textile material in localized areas with a dye rate controlling agent which significantly increases or decreases the amount of dye adsorption, said agent being selected from the group consisting of methylnaphthalene, phenylphenol, a condensation product of resorcinol and formaldehyde, and a condensation product of benzyl chloride and sulfonated naphthalene;

(b) fixing said dye rate controlling agent on said polyamide textile material by heat treatment;

(c) washing said material so as to form areas which vary in the amount of dye adsorption; and

(d) dip dyeing said material, using an anion dyestuif.

2. A method of producing an ornamental multitone effect on polyamide textile materials, which includes the sequence of steps:

(a) padding the surface of said polyamide material with a dye rate controlling agent which significantly increases or decreases the amount of dye adsorption, said agent being selected from the group consisting of methylnaphthalene, phenylphenol, a condensation product of resorcinol and formaldehyde, and a condensation product of benzyl chloride and sulfonated naphthalene;

(b) said controlling agent being applied to different areas of said textile material in at least two different amounts so that said textile material will adsorb at first dye rate controlling agent which significantly increases the amount of dye adsorption, said first dye rate controlling agent being selected from the group consisting of methylnaphthalene and phenylfect on polyamide textile materials, which includes the sequence of steps:

(a) padding different areas of the surface of said polyamide textile material with a solution containing an agent which significantly increases or decreases the amount of dye adsorption for controlling the rate of least two different amounts of dye; dyestuffs into polyamide textile materials, said agent (c) fixing said dye rate controlling agent on said texbeing selected from the group consisting of methyltile material by heat treatment; naphthalene, phenylphenol, a condensation product of (d) washing said material so as to form areas which resorcinol and formaldehyde, and a condensation vary in the amount of dye adsorption; and product of benzyl chloride and sulfonated naphtha- (e) dip dyeing said material, using an anion dyestuff. lene; 3. A method of producing an ornamental multitone (b) fixing said dye rate controlling agent on said texeifect on polyamide textile materials, which includes the tile material by heat treatment; sequence of steps: (c) washing said material so as to form areas which (a) padding areas of the surface of said polyamide vary in the amount of dye adsorption; and

textile material with a printing paste containing a (d) dip dyeing said material, using an anion dyestuff.

7. A method of producing an ornamental multitone effect on polyamide textile materials, which includes the sequence of steps:

(a) padding different areas of the surface of said polyphenol; padding different areas of the surface of said amide textile material with a printing paste containpolyamide textile material with a printing paste coning a retarding agent which significantly decreases the taining a second dye rate controlling agent Which amount of dye adsorption onto said polyamide textile significantly decreases the amount of dye adsorption, material in different concentrations, said agent being said second dye rate controlling agent being selected selected from the group consisting of a condensation from a condensation product of resorcinol and formproduct of resorcinol and formaldehyde, and a conaldehyde, and a condensation product of benzyl densation product of benzyl chloride and sulfonated chloride and sulfonated naphthalene; naphthalene;

(b) fixing said dye rate controlling agents on said texfixing said printing paste on said t til t i l tile material by heat treatment; y heatfreatment;

(c) washing said material so as to form areas which Washing Said material 80 as to form areas which vary in the amount of dye adsorption; and (d) dip dyeing said material, using an anion dyestuif. 4. A method of producing an ornamental multitone vary in the amount of dye adsorption; and (d) dip dyeing said material, using an anion dyestuff. 8. A method of producing an ornamental multitone effeet on polyamide textile materials, which includes the effect on polyamide textile materials, which includes the sequence of steps:

sequence of steps: 4

(a) padding areas of the surface. of said polyamide textile material with a solution containing a first dye rate controlling agent which significantly increases the amount of dye adsorption, said first dye rate controlling agent being selected from the group consist- (a) padding different areas of the surface of said polyamide textile material with a solution containing a retarding agent which significantly decreases the amount of dye adsorption onto said polyamide textile material in different concentrations, said agent ing of methylnaphthalene and phenylphenol; padding being selected from the PP COIlSiSting Of a 0 11- different areas of the surface of said polyamide texdensatlon P f of resorclnol and formaldehyde, tile material with a solution containing a second dye and a condensatlon Productof 3 Chloride a rate controlling agent which significantly decreases sulfoflated'naphthfllefle; the amount f dye adsorption said Second dye rate (b) fixing said solution on sald textile material by heat controlling agent being selected from a condensation treatmeflt; product of resorcinol and formaldehyde, and a conwashmg Sald matenal so as to f areas W h densation product of benzyl chloride and sulfonated y In amqlmt of y P a naphthalene; (d) dip dyeing said material, using an anlon dyestuif. (b) fixing said dye rate controlling agents on said poly- References Cited amide textile material by heat treatment; (c) washing said material so as to form areas which UNITED STATES PATENTS vary in the amount of dye adsorption; and 3, 79,483 4/1965 Millson et a1. 821 B (d) dip dyeing said material, using an anion dyestutf.

OTHER REFERENCES 5. A method of producing an ornamental multitone ef- Vickerstaif, The Physical Chemistry of Dying, 2nd

fect on polyamide textile materials, which includes the Ed., (1954) Interscience, N.Y., pp. 441, 443, 478.

sequence of steps:

(a) padding different areas of the surface of said polyamide textile material with a printing paste containing an agent which significantly increases or decreases the amount of dye adsorption onto polyamide textile materials, said agent being selected from the group consisting of methylnaphthalene, phenylphenol, a condensation product of resorcinol and formaldehyde,

NORMAN G. TORCHIN, Primary Examiner J. WINKELMAN, Assistant Examiner US. Cl. X.R. 

